Hf conversion of hydrocarbons



Oct. 17, 1950 A. P. LIEN HAL up couvmsxon oF HYnRocARBoNs Filed' July1o, 1947 Patented Oct. 17, 1950 nr ooNveasioN or mnocAanoNs Arthur P.Lien, Hammond, Ind., and Bernard L. f Evcring, Chicago, Ill., assignorsto Standard Oil Company, Chicago, Ill., a corporation oi' IndianaApplicatie July 1o, 1941, sensi No. ramona s claim. (ci. 19e- 52) l Thisinvention relates to the conversion of hyand it pertains moreparticularly to the conversion of high boiling hydrocarbons for theproduction of hydrocarbons in the gasoline and/or Diesel fuel boilingrange and one or more valuable tars. In its more specific aspects theinvention relates to a combination process wherein cnc step involves theseparation of substantially HF- insoluble polycyclic aromatichydrocarbons such as alkyl naphthalenes from saturated hydrocarbons by aprocess which involves intermolecular chemical condensation of saidaromatic hydrocarbons to produce HF-soluble polynuclear aromatichydrocarbons which are extracted from said saturated hydrocarbons. Thechemical condensation and the `extraction steps are performed in amedium consisting essentially of liquid anhydrous hydrogen uoride whichfunctions as a catalyst in the chemical reaction and as a solvent in theextraction operation. Also, the invention may eliminate sulfur at thehigher temperatures by splitting out HrS from the organic sulfurcompounds to form unsaturated hydrocarbons, although some of the organicsulfur compounds may be simply extracted by the hydrogen fluoride. Thechemical condensation per se is claimed in copending application Ser. No135,166, filed December 27, 1949, as a continuation in part of copendingapplication Ser. No. 760,061, which was filed on even date hereof and inwhich condensation by combined use of HF and BF: is claimed.

An object of the invention is to provide a method and means forimproving the cracking suscep^ drocarbons by use of a hydrogen fluoridecatalyst In practicing our invention we employ a multistage operationwherein the incoming charging stock is first contacted under mildoperating conditions for thepurpose of condensing and/or removingchemically condensable aromatics (and sulfur compounds) as an aromatictar in high specific gravity while effecting only a slight amount ofcracking so that a gas oil is produced which is substantially free fromsulfur and condensable aromatics and which contains only a small amount,preferably less than 5%, of hydrocarbons of the gasoline boiling range.The gas oil from this first stage, either before or after removal ofgasoline boiling range components, is then contacted with hydrogeniiuoride under cracking conditions in a second stage to produce gas,gasoline ,(and/or Diesel fuel) and an entirely different type of tarthan is produced in the first stage. A portion `of the tar from thesecond reaction stage may be recycled thereto for increasinggasolineyields and rate of conversion while another portion of the tarfrom the `second stage is separated from catalyst to yield a valuableby-product having unique drying propquired. A further object is toobtain good yields erties. These and other features of the inventionwill bemore clearly apparent from the following detailed description ofa specific example thereof read in conjunction with the accompanyingdrawing which is a schematic ow diagram of a system for converting anEast Texas gas oil into gas, gasoline, a valuable oleiinic tar and atarcomprising principally condensed ring polynuclear aromatichydrocarbons.

While any aromatic and sulfur-containing charging stock may be employed,such charging stock should preferably be higher boiling than -gasolineand the preferred charge is a gas oil or reduced crude containingchemically condensable aromatic hydrocarbons. The invention will bedescribed as applied to the conversion of a 37 API gravity East Texasgas oil which is introduced. into thesystem from source II) by pump I Iand charge line I2 to first reactor I3. Hydrogen fluoride is introducedfrom storage tank I4 by pump I5 and lines I6 and I2 to said iirstreactor in such amounts that the total charge entering the first reactorwill contain about l0 to 200%,

`preferably 15 to 50% hydrogen fluoride by volume based on gas oilcharged. Reactor I3 is maintained at a conversion or condensingtemperature in the range of 200 to 375 F., preferably about 250 to 330F. by preheating the gas oil charge or` supplying heat to the reactor inany other known manner. First reactor I3 is operated under a pressuresuiiicient to maintain liquid 3 phase conversion conditions. i. e.within a range of about 250 to 1000 p.'s. i., or preferably about 500 to800 p. s. i. The time of contact in the reactor should be relativelylong, usually'within the range of about 20 to 200 minutes (the lowertemperatures requiring longer Contact times); with eflicient contactingmeans for `securing intimate contact, the time lat 330 F. maybeabout anhour. Aromatic condensation without excessive cracking When the HFconcentration is high the contact time and temperature used will berelatively, low. Conversely higher temperatures and longer contact timeswill be used at lower HF concentra-ftins. The conditions should 'be suchas to eifect condensation of condensable aromatics and removal of sulfurso that the hydrogen-fluoride insoluble material will be chiefly aparafnic gas oil, substantially free from condensable aromatics andsulfur and containing only a small amount, preferably less than ofgasoline-boilingrange hydrocarbons, including benzene andmethylbenzenes. l

vThe reactor itself may be a stirred autoclave, .a packed or unpackedtowerwith or without mixving orices, a circulating system of the typecommonly employed for effecting sulfuric acid alkylation, or any othereffective contacting means. Since no invention is claimed in thecontacting means per se. it will not be described in further detail.

vThe efliuent from the first reactor is withdrawn by line II through acooler I8 (although such cooler may not be necessary) and introducedinto settler I9 which may operate at substantially conversion pressurebut at a temperature sufficiently low to insure the separation of thehydrogen fluoride phase as a lower layer, e. g. a temperature in therange of about 100 to 250 F. It should be understood that more than onesettler may be employed and that separation may rst be effected atsubstantially reaction temperature and the hydrogen fluoride phase fromthis high temperature separation may be subsequently separated at alower temperature. The separated hydrogen fluoride layer is withdrawnfrom the settler by line 20 and a portion of it may be recycled by line2i andpump 22 to reactor inlet line I2 in order to decrease the amountof hydrogen fluoride that must be supplied from storage tank I4 and tomaintain in reactor I3 about 25 to 50% or more, preferably at leastabout 30% by weight. of tar (hydrogen fluoride soluble hydrocarbons)based on the hydrogen fluoride in the reactor. At the beginning of theoperation all of the hydrogen uoride-tar material withdrawn through linemay thus be recycled to the reactor for the dual purpose of improvingthe catalyst effectiveness in the reactor and for degrading said tar andobtaining maximum yields of hydrogen fluoride-insoluble hydrocarbonssuch as gas oil therefrom. When desired equilibrium conditions arereached and there is for example about 40% by weight of tar in reactorI3 based on hydrogen uoridetherein, a sufilcient amount of the liquidwithdrawn through line 20 is introduced through pressure reducing valve23 into tar stripper 24 to maintain the substantially constant amount oftar in the reactor and to remove any excess tar.

The excess tar may be simply stripped of hydrogen fluoride by heatingmeans 25 in the base of a conventional stripping tower so that a iirsttar is removed by line 26 which tar may be characterized by a specificgravity of about .98 and an is dependent on several variables.-

1 series of coils to provide the necessary holding time) and then ashedinto tar or coke stripper 24 for hydrogen fluoride removal. If such acoking operation is employed, butane or other gas may be introduced atthe base of tower 2l for stripping and removing hydrogen fluoride fromcoke particles and for providing a supporting and fluidizing medium sothat the' solids may be removed in fluidized condition through line 26.In either vcase the hydrogen fluoride and any light hydrocarbons whichmay be associated therewith are withdrawn overhead from the tar stripperthrough line 23 to product stripper 30.

The hydrocarbon phase in settler I9 ows over baiile'I and is withdrawnthrough line 32. The

. material thus withdrawn consists chiefly of substantiallyaromatic-free gas oil and perhaps a small amount ofgasoline-boiling-range 'components containing dissolved hydrogeniluoride. The withdrawn stream of these materials may be introducedv bylines 33 and 29 to product stripper 30 or may be introduced by-lines 34and 35 to second reactor 36. If it is introduced into the productstripper 30 via lines 33 and 29 the dissolved hydrogen fluoride isremoved therefrom by heater 31 and/or stripping gas introduced throughline 38 and the hydrogen fluoride-free products are withdrawn by line 39to fractionating d system diagrammatically illlustrated by tower 40,wherein a normally gaseous stream containing butanes is` withdrawnthrough line 4I, a light naphtha stream .through line 42, a heavynaphtha stream through line 43 and a gas oil stream through line 44.v'Thegas oil stream or at least a substantial portion thereof may thenbe returned by pump 45 and lines 46 and 35 to second reactorv 36. Thusin either type of operation a substantially aromatic-free gasoilproduced in first reactor I3 is subsequently charged to second reactor36. The substantially aromaticfree gas oil produced in our process or afraction thereof is useful per se as a superiorDiesel fuel; Also suchgas oil is particularly suitable as a charging stock for catalyticcracking with solid catalysts of the silica alumina or silica magnesiatype in the systems and under the conditions generally known to the artin fixed bed (Houdry) moving bed (Thermofor Catalytic Cracking) orpowdered catalyst (Fluid) processes; this particular gas oil is not onlyremarkably amenable to such cracking processes but it can be processedwith less carbon deposition than would other-l wise be' obtained. Thissubject matter is claimed in our copending application Ser. No. 168,112,filed July 14, 1950, as a continuation-impart of the present applicationand also as-a continua? tion-in-part of our copending application Ser.No. 718,038, filed December 23, 1946.

We control the amount of gasoline boiling range non-condensablearomatics introduced into the second reactor by passing through line 33controlled amounts of the stream from line 32' to stripper 30 and thenceby line 39 to fractionator 40 where any mononuclear aromaticsof'gasoline boiling range, formed by scission of side chains fromaromatic nuclei in the first reactor, are removed as a part of thenaphtha stream. The remainder of the stream in line 32 is sent directlyby lines 34 and 35 to the second reactor. This proportioning of thestream in line 32 keeps the amount of aromatics, which tend to inhibitcracking in the second reactor. at a desirably low figure, that is,about 0.05 to 5% or less.

Hydrogen fluoride is withdrawn from storage tank I4 and introduced bypump 41 and line 48 to line 35 and second reactor 36, the amount ofhydrogen fluoride thus introduced being such that the total streamentering the second reactor contains about to 400%. preferably about 50%to 200% by volume based on total gas oil (or gas oil plus gasoline)charged thereto. The second reactor may be of the same type as the firstreactor, although it may be somewhat smaller in size. Conversionconditions in the second reactor 36 may be more severe than those in thefirst reactor I3, particularly if aromatics such as benzene of thegasoline boiling range are included in the charge. The temperature inreactor 36 should be in the range of 250 to 500 F., preferably 300 to400 or about 350 F. The time of contact should be relatively short. i.e. Within the range of about 2 to 60 minutes, preferably 2 to 20minutes, for example about 5 to l5 minutes. The weight space velocitymay be about .5 to 5 or preferably about 1 to 2 parts by weight of oilcharged per hour per part of hydrogen fluoride in the conversion zone.The reaction is primarily cracking and hydrogen transfer for productionof isobutane, gasoline, and/or Diesel fuel and a valuable tar.

The product stream leaves the second reactor through line 49 and passesthrough cooler 50 to settler 5I wherein a hydrogen fluoride-tar phaseseparates out as a lower layer and is withdrawn through line 52. At thebeginning of the operation, all of the liquid withdrawn through line 52may be recycled by line 53 and pump 54 to line 35 and reactor 36 untilthe total amount of tar in the second reactor is within the range ofabout to 40%, or preferably about 25%, by weight based on the hydrogenfluoride contained in the second reactor. Thereafter, the amount ofmaterial recycled through line 53 is just suilicient to maintain the tarratio in the reactor substantially constant, and the excess tar isintroduced by line 55 to tar stripper 56 which is provided with asuitable heater 51 for removing the hydrogen fluoride. This tar stripper56 like tar stripper 2l may be operated at a temperature in the range of350 to 550?. and at a relatively low pressure of the order of about 5 to50 pounds per square inch gage. An alternative method of operation,designed to increase the yield and improve the drying oil properties ofthe tar, is to operate the second reactor on a once-through basis withrespect to tar.

The substantially hydrogen iluoride-free second tar withdrawn throughline 58 is quite different in character from the iirst tar withdrawnthrough line 26. The second tar may have a specific gravity ofapproximately .90 to .94 and an iodine number of about 250 to 350 ormore. It does not contain appreciable amounts of condensed aromatics orsulfur, but is a highly unsaturated polyene material having dryingproperties and is useful in the preparation of paints, coatingmaterials, and the manufacture of synthetic plastics and resins.

The overhead from tar stripper 56 is passed 6 by line 69 to productstripper 30. The upper hydrocarbon layerwfrom settler 6I passes overbaiile 60 and is withdrawn through line 6I to line 58 and productstripper-30. The product stripper 30 is operated under such conditionsthat substantially all of the HF is removed overhead as a butaneazeotrope. the overhead stream passing through line 62 and cooler 63 toseparator 64 which may operate at condenser water temperature,preferably below 100 F. The relatively pure hydrogen fluoride whichseparates out as a lower layer is introduced by line 65 into storagetank I4, any required makeup hydrogen iiuoride being introduced throughline 66.

Butane (chiey isobutane) flows over baille 61 and is withdrawn by pump58. A part of this butane may be introduced at a low point in stripper30 by line 38 as hereinabove described. The rest of the withdrawn butanestream may pass by line 69, line 10, and line I2 tofirst reactor I3 inorder to facilitate tar degradation. At least a portion of the butanemay be passed by lines 69, 1I, and 35 into second reactor 36 wherein it`may serve to prevent excessive gas production. Should it be required tovent any gases lighter than butane from the system, such gases may beremoved from the top of settler 64 through line 12; if and when suchventing is necessary the vented gases may be scrubbed Awith tar, e. g.from line 26, in order to remove the last traces of hydrogen fluoridefrom the vented gases and the hydrogen uoride-containing tar may then bereturned to first reactor I3.

In the example hereinabove described. it will be noted that hydrocarbonsfrom both tar strippers and from at least one of the product settlersare all introducedinto one and the same stripper 30 and the butanes maybe returned if desired from settler 64 to first reactor I3. Analternative procedure is to operate settler I9 at a soiliciently lowtemperature and pressure so that at least a portion of the overhead fromtower 30 may be introduced into settler I9. Similarly by operatingsettler 5I at sufiiciently low temperature and pressure, at least aportion of the overhead from product stripper 30 may be introducedthereto. An advantage of the system illustrated in the drawing is thatsettlers I9 and 5I may be operated at substantially conversion pressure,thus minimizing, if not entirely eliminating, the pumping required forrecycle through lines 20 and 52 respectively.` The system illustrated inthe drawing also provides for the removal of net butane production fromthe base of product stripper 30 since the azeotropicdistillation ofhydrogen fluoride from products in stripper 30 will permit the removalof the net butane production with the bottoms stream while substantiallyAall the hydrogen uoride is taken overhead as a butane azeotrope.

While we have described a specific example of the invention inconsiderable detail, it should be understood that the invention is notlimited to the specific system or conditions therein. described sincemany alternative arrangements and operating conditions will be readily`apparent from the above description to those skilled in the art.Promoters such as boron triiluoride may be employed to enhance theactivity of the catalyst and such promoters are particularly desirablewhen it is desired to eiect the cracking of naphthenes. Engineeringdetails such as valves, pumps, heat exchangers, etc. have been largelyomitted from the schematic drawings and conventional reiining methodsare to be employed for fractionation and stripping where such operationsare schematically illustrated in the drawings.

We claim:

1. The method of obtaining valuable products from a hydrocarbon chargingstock which is higher boilingythan gasoline and which containssubstantial amounts of polycycllc aromatics which are insoluble inhydrogen fluoride but which are condensable in the presence of hydrogenfluoride into higher molecular weight hydrogen iluoride solublehydrocarbons with liberation of hydrogen, which method comprisestreating said charging stock with a catalyst consisting essentially ofhydrogen fluoride in a first conversion zone under conditions foreffecting intermolecular chemical condensation of said polycyclicaromatic hydrocarbons into hydrogen fluoride-soluble condensed aromaticsof higher molecular weight with simultaneous liberation of hydrogen,separating the condensed polycyclic aromatlcs and the hydrogen fluoridein which they are dissolved from hydrogen fluoride-insolublehydrocarbons consisting essentially of a gas oil which is relativelyfree from condensable aromatics, subsequently contacting said gas oilwith a catalyst consisting essentiallyof hydrogen iluoride underconditions for converting said gas oil into hydrocarbons of the gasolineboiling range and a. high boiling, highly oleflnic, hydrogenfluoridesoluble product, substantially free from condensed aromatics, separatingthe olenic product and the hydrogen fluoride in which it is dissolvedfrom hydrocarbon products insoluble in hydrogen fluoride and separatelyremoving hydrogen fluoride associated, respectively, with the condensedpolycyclic aromatic material, the highly olefinic product and thehydrocarbon products insoluble in hydrogen iluoride.

2. The method of claim l wherein a small amount, but less than ofhydrocarbons of the gasoline boiling range is produced as well as gasoil in the first conversion zone, 'which includes the further step orseparating said gasoline boiling range hydrocarbons from said gas oilbefore said gas oil is introduced into said second conversion zone.

3. The method of claim l which includes the step of introducing directlyinto the second conversion zone substantially all of the hydrogenfluoride insoluble products from the first conversion zone.

4. The method of treating a hydrocarbon charging stock which is higherboiling than gasoline and which contains substantial amounts ofpolycyclic aromatics which are insoluble in hydrogen fluoride but whichare condensable in the presence of hydrogen fluoride into highermolecular weight hydrogen fluoride soluble hydrocarbons with liberationof hydrogen, which method comprises reacting said charging stock in afirst conversion zone under aromatic condensation conditions at'atemperature in the range of 200 to 375 F. at a pressure sufficient tomaintain liquid phase conversion conditions and in the range of 250 to1000 pounds per square inch and for a time of contact within the rangeof 20 to 200 minutes while introducing about to 300% by volume ofhydrogen fluoride per volume of hydrocarbon introduced into said firstconversion zone; separating hydrogen fluoride and tar from productsincluding a gas oil portion leaving the first conversion zone;subsequently contacting at least the gas oil portion of said productswith a catalyst consisting essentially of hydrogen fluoride in a secondconversion zone under cracking conditions including a temperature in therange of 250 to 500 F.. a pressure sufficient to maintain liquid phaseconversion conditions, a catalyst-to-oll weight ratio in the range of.5:1 to 5:1 and a contact time in the range of 2 to 60 minutes;separating a, second tar from hydrogen fluoride insoluble productsproduced in the second conversion zone; separately stripping the tworemoved tars. and stripping at least thehydrogen fluoride insolubleproducts from the second conversion zone-in order to remove hydrogenfluoride therefrom; and recovering hydrocarbons of the gasoline boilingrange from stripped products.

5. The methodof converting n, high boiling hydrocarboncharging stockcontaining chemically condensable polycyclic aromatics chiefly intothree main products, namely, a high specific gravity tar, a lowerspecific gravity high boiling highly olenic product substantially freefrom` condensed aromatics, and gasoline boiling rangel hydrocarbons,which method comprises treating said charging stock with a catalystconsisting essentially of hydrogen fluoride under conditions foreffecting condensation of condensable aromatics into higher` molecularweightJ hydrocarbons with liberation of hydrogen, separating from thereaction products a hydrogen fluoride layer containing said condensedaromatics from a hydrogen fluoride insoluble fraction, strippinghydrogen fluoride from said condensed aromatics and returning saidhydrogen fluoride to the system, mixing additional catalyst consistingessentially of hydrogen lfluoride with the hydrogen fluoride insolublelayer and contacting said mixture at a temperature of at least about 300F., at a pressure sumcient to maintain liquid phase conversionconditions with a hydrogen fluorideto-oil weight ratio of about .5:1 to5:1 for a period of about 2 to 2O minutes to effect a conversion intolow boiling parainic hydrocarbons and high boiling olenic hydrocarbons,the latter being associated with the hydrogen fluoride, separating theparafhnic hydrocarbons from the hydrogen fluoride-olelnic hydrocarbonmixture, removing hydrogen fluoride from the latter to produce a highboiling highly olefinic product substantially free from hydrogenfluoride and stripping hydrogen fluoride from the parafiinichydrocarbons.

6. The method of obtaining valuable products from a hydrocarbon chargingstock which is higher boiling than gasoline and which containssubstantial amounts of polycyclic aromatics.

Iwhich are insoluble in hydrogen fluoride but which are condensable inthe presence of hydrogen fluoride into higher molecular weighthydrocarbons with liberation of hydrogen, which method comprisestreating said charging stock with a, catalyst consisting essentially ofhydrogen fluoride in a first conversion zone under conditions foreffecting intermolecular chemical condensatlon of said polycyclicaromatic hydrocarbons into hydrogen fluoride-soluble condensed aromaticcompounds of higher molecular weight with simultaneous liberation ofhydrogen, separating the condensed aromatic compounds, together with thehydrogen fluoride in which they are dissolved, from hydrogenfluoride-insoluble hydrocarbons consisting essentially of a gas oilwhich is relatively free from condensable aromatics, subsequentlycontacting said gas oil with a cracking catalyst which consistsessentially of hydrogen fluoride under conditions for effecting as the`predominant reaction a conversion of said gas oil into hydrocarbons ofthe gasoline boiling 9 range and separating said last named hydrocarbonsfrom higher boiling and lower boiling components.

7. The method of claim 6 wherein the first conversion zone is maintainedat a temperature in the range of about 200 F. to 375 F., under apressure in the range of about 250 to 1000 pounds per square inch andfor a time of contact in the range of about 20 to 200 minutes with anamount of hydrogen uoride in the range of about 10 to 300 volume percent based on stock charged.

8. The method of claim 6 wherein the gas oil contains about .05 to 5 percent ofaromatics.

ARTHUR P. LIEN. BERNARD L. EVERING.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,872,446 Halloran et ai Aug. 16,1932 1,881,901 Osmer 1 Oct. 11, 1932 2,258,394 Tinker et al. Oct. 7,1941 2,304,289 Tongberg Dec. 8, 1942 2,343,841 Burk Mar. 7, 19442,378,762 Frey June 19, 1945 2,405,995 Burk Aug. 20, 1946 2,454,615Ridgway et al Nov. 23, 1948 l5 809 and 810. Published by Heath 8: Co.,Boston,

1. THE METHOD OF OBTAINING VALUABLE PRODUCTS FROM A HYDROCARBON CHARGINGSTOCK WHICH IS HIGHER BOILING THAN GASOLINE AND WHICH CONTAINSSUBSTANTIAL AMOUNTS OF POLYCYCLIC AROMATICS WHICH ARE INSOLUBLE INHYDROGEN FLUORIDE BUT WHICH ARE CONDENSABLE IN THE PRESENCE OF HYDROGENFLUORIDE INTO HIGHER MOLECULAR WEIGHT HYDROGEN FLUORIDE SOLUBLEHYDROCARBONS WITH LIBERATION OF HYDROGEN, WHICH METHOD COMPRISESTREATING SAID CHARGING STOCK WITH A CATALYST CONSISTING ESSENTIALLY OFHYDROGEN FLUORIDE IN A FIRST CON-P VERSION ZONE UNDER CONDITIONS FOREFFECTING INTERMOLECULAR CHEMICAL CONDENSATION OF SAID POLYCYCLICAROMATIC HYDROCARBONS INTO HYDROGEN FLUORIDE-SOLUBLE CONDENSED AROMATICSOF HIGHER MOLECULAR WEIGHT WITH SIMULTANEOUS LIBERATION OF HYDROGEN,SEPARATING THE CONDENSED POLYCYCLIC AROMATICS AND THE HYDROGEN FLUORIDEIN WHICH THEY ARE DISSOLVED FROM HYDROGEN FLUORIDE-INSOLUBLEHYDROCARBONS CONSISTING ESSENTIALLY OF A GAS OIL WHICH IS RELATIVELYFREE FROM CONDENSABLE AROMATICS, SUBSEQUENTLY CONTACTING SAID GAS OILWITH A CATALYST CONSISTING ESSENTIALLY OF HYDROGEN FLUORIDE UNDERCONDITIONS FOR CONVERTING SAID GAS OIL INTO HYDROCARBONS OF THE GASOLINEBOILING RANGE AND A HIGH BOILING, HIGHLY OLEFINIC, HYDROGENFLUORIDESOLUBLE PRODUCT, SUBSTANTIALLY FREE FROM CONDENSED AROMATICS, SEPARATINGTHE OLEFINIC PRODUCT AND THE HYDROGEN FLUORIDE IN WHICH IT IS DISSOLVEDFROM HYDROCARBON PRODUCTS INSOLUBLE IN HYDROGEN FLUORIDE AND SEPARATELYREMOVING HYDROGEN FLUORIDE ASSOCIATED, RESPECTIVELY, WITH THE CONDENSEDPOLYCYCLIC AROMATIC MATERIAL, THE HIGHLY OLEFINIC PRODUCT AND THEHYDROCARBON PRODUCTS INSOLUBLE IN HYDROGEN FLUORIDE.